CARBOXYLIC ACIDS AND THEIR DERIVATIVES. 3. Predict the relative acidity and basicity of compounds and ions. Important criteria include:

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1 CARBXYLIC ACIDS AND TEIR DERIVATIVES A STUDENT SULD BE ABLE T: 1. Give the IUPAC name given the structure, and draw the structure given the name, of carboxylic acids and their metal salts, acyl chlorides, esters, amides, and nitriles. Also, draw the structure given any of the following common names: phthalic, oxalic, malonic, succinic and glutaric acids; formic and acetic acids and their salts, chlorides, esters, and amides; and acetic and phthalic anhydrides. 2. Predict the solubility of carboxylic acids and their derivatives in water and in various acidic and basic solutions. Compounds containing previously studied functional groups may also be included. 3. Predict the relative acidity and basicity of compounds and ions. Important criteria include: The normal order of acidity of functional groups is: RS 3 > RC 2 > Ar > RS > 2 > R > RC C > RN 2 > R Within a functional group family, conjugate acids are stronger acids than conjugate bases. That is: 3 X + > 2 X > X Within a functional group family, electron-donating (activating) groups give stronger bases, and electron-withdrawing (deactivating) groups give stronger acids. The effect of an electron-withdrawing group depends on its proximity to the carboxylic acid moiety. The stronger the acid, the weaker its conjugate base (and vice versa). 4. Predict the product of reactions giving rise to carboxylic acids (many of these are review), and the reactions of carboxylic acids and their derivatives, when given starting materials and reaction conditions. Important reactions include: Acid-base reactions. Stronger acid + stronger base weaker acid + weaker base. xidation of 1 alcohols, aldehydes, alkylbenzenes and alkynes. ydrolysis of nitriles. Reductions with lithium aluminum hydride (LA). Carboxylation (carbonation) of Grignard reagents. Nucleophilic acyl substitution (interconversion of carboxylic acids and their derivatives). Reactions of acyl halides with R 2 CuLi and LiAl(R) 3 to make ketones and aldehydes. 5. Predict and explain experimental results from your knowledge and understanding of nucleophilic acyl substitution mechanisms. 6. Use the reactions of #4 above, plus others learned earlier, to propose syntheses of carboxylic acids and related compounds. 7. Predict and interpret spectra and solubility test results to identify unknown carboxylic acids and their derivatives.

2 Solubility Tests for Monofunctional Compounds This section tells you how to predict results for known compounds and use results to classify unknowns. Some are useful as stand-alone tests, but compounds that dissolve in water are soluble in all of the other reagents listed here; follow the whole scheme to get the best possible information. For these tests, soluble means one drop of unknown will dissolve in one ml of solvent. Compounds that are insoluble may still dissolve in a large volume of water. Solubility in water If a compound is soluble in water, it is a compound of about four carbons or less that contains N or (or it may contain more than one functional group). If the compound contains five or six carbons, it may be soluble. If it contains six carbons or more, it will be insoluble if there is only one functional group, but it may be soluble with multiple groups. If the compound is soluble, the solution is then tested with litmus paper. If the solution turns blue litmus red, the unknown is a carboxylic acid (RC 2 ). If the solution turns red litmus blue, the unknown is an amine (RN 2, R 2 N, or R 3 N). If the solution is neutral to litmus, the unknown includes a neutral - or N-containing functional group such as an alcohol, ether, aldehyde, ketone, ester, or amide. If the compound is insoluble in water, go on to the next solubility test. Solubility in 5% Na If the compound is soluble in 5% Na but insoluble in water, it is acidic, either a phenol (Ar) or a carboxylic acid (RC 2 ). This is reaction solubility, not like-dissolves-like solubility; the alkaline test solution reacts with acidic compounds to give ionic, water-soluble products. You must run the water solubility test first for this test to be useful; 5% Na is 95% water, and compounds that dissolve in water also dissolve in 5% Na because of that. To distinguish between phenols and carboxylic acids, you can use the NaC 3 solubility test (next). If the compound is insoluble in 5% Na, go to the 5% Cl solubility test. Solubility in 5% NaC 3 Sodium bicarbonate is a weaker base than Na. This is another reaction-solubility test; bicarbonate ion reacts with carboxylic acids but not with phenols to produce water-soluble salts. The reaction also gives carbon dioxide, and these bubbles are visible, making this a useful standalone test for carboxylic acids. Solubility in 5% Cl This is yet another reaction-solubility test. Basic organic compounds (amines) react with the acid to give water-soluble products. As with the 5% Na test, it is necessary to test with water first, for the same reason. If the compound is insoluble in 5% Cl, go to the next (and last) solubility test. Solubility in concentrated 2 S 4 Alkenes, alkynes, and compounds that contain N and are protonated by this extremely powerful acid, and the products of these reactions dissolve. Concentrated sulfuric acid is approximately 94% acid. Compounds that contain only alkyl groups, halogen atoms, and benzene rings (R, RX, Ar, ArX) will fail to dissolve.

3 To best prepare for this module, please work Chapter 21 Skill Builder problems in the textbook. A STUDENT W AS MASTERED TE BJECTIVES FR TIS UNIT SULD BE ABLE T SLVE TE FLLWING PRBLEMS AND RELATED NES: 1.1 Draw the structure of each of the following compounds. a) malonic acid b) acetic anhydride c) sodium formate d) acetonitrile e) phthalic anhydride f) dimethyl succinate 1.2 Name each of the following compounds. 2.1 Which of the following compounds is most soluble in water? a) C 3 C 2 CC 3 b) C 3 CC 2 C 3 c) C 3 C 2 C d) C 3 (C 2 ) 3 C 2.2 Which of these compounds (a) does not dissolve in 2 but does dissolve in Na (aq)? (b) does not dissolve in 2 but does dissolve in Cl (aq)? a) C 3 C 2 C 2 C 2 C 2 C 3 b) C 3 C 2 C 2 c) C 3 C 2 NC 3 d) C 6 5 C 2 C 2 e) C 6 5 C 2 N 2 f) C 6 5 C Which of the following compounds is the strongest acid?

4 3.2 Which of the following compounds is the weakest acid? 3.3 Which of the following compounds is the weakest base? 3.4 Which of the following compounds is the strongest acid? 4. Predict the product(s) of each of the following reactions.

5 4. Reactions (Continued): h) 1. LA Propose a mechanism for each of the following reactions.

6 5. Mechanisms (Continued): 6. Propose a synthesis of each of the indicated compounds from the given starting material and any other needed reagents. a) methyl benzoate from toluene d) benzamide from styrene

7 6. Synthesis (Continued): f) ethyl benzoate from bromobenzene 7.1 For these questions, choose the answer from the list of possible compounds at the end of the section. a) Which of the following compounds has a broad peak in its IR spectrum in the cm -1 region, and gives an aqueous solution that turns blue litmus red? b) Which one gives a broad, strong absorption peak in its IR spectrum near 3400 cm -1, is insoluble in water and 5% Na (aq), but is soluble in conc. 2 S 4? c) Which one is insoluble in water, and soluble in both Na (aq) and NaC 3(aq)? d) Which one has only one peak in its proton NMR spectrum? The possible answers are:

8 7.2 Identify the following C unknown from the given spectroscopic information. IR: broad peak in cm -1 region, and a peak at 1715 cm -1 1 NMR: triplet, δ 1.27, 3 quartet, δ 3.66, 2 singlet, δ 4.13, 2 singlet, δ 10.95, Which of the compounds below fits these data for C ? 1 NMR: doublet, 1.4, 6 multiplet, 2.2, 1 doublet, 4.1, 2 multiplet, 7.1, 5 SLUTINS T SAMPLE PRBLEMS: 1.1 a) malonic acid b) acetic anhydride c) sodium formate d) acetonitrile e) phthalic anhydride f) dimethyl succinate

9 1.2 a) 3,3-dimethylbutanoic acid b) ethyl chloroethanoate (or ethyl chloroacetate) c) 2-phenylpropanamide d) benzoyl chloride e) N-ethyl-N-methylbutanamide f) cyclobutane carboxylic acid 2.1 c 2.2 a) c b) d 3.1 b 3.2 a 3.3 b 3.4 c 4. Predicting the products of reactions. b) Br + Mg ether C C 2

10 4. 5. Mechanisms:

11 5. c) + C C C + 3 C weak nucleophile C 3 C C 3 C 3 C C C (Continued on next page)

12 5.d) (Continued from previous page) + C 3 C 2 C 2 C C 2 C 3 C 2 C 3 :B C 2 C 3 + C 3 C 2 C 3 6. Propose a synthesis. d) KMn 4 -, 2, heat C SCl 2 2. xs N 3 N 2

13 a) a b) e c) c d) b 7.2 C 3 C 2 C 2 C a

14 Name Seventh Drill Test (Sample A) rganic Chemistry 2220D Answer All Questions 1. Which of the following compounds is the strongest acid? 2. Draw: benzyl benzoate 3. Name: 4. Predict the major product(s) (if any) of each of the following reactions. 5. Propose a mechanism for the following reaction. 6. Propose syntheses, from the given starting material and any other needed reagents. a) benzamide from benzyl alcohol b) C 3 C 2 C 2 C= from C 3 C 2 C 2 CCl

15 Name Seventh Drill Test (Sample B) rganic Chemistry 2220D Answer All Questions 1. a) Draw: N,N-diethylbenzamide b) Draw: benzyl propanoate c) Name: d) Name: 2. Write an acceptable mechanism for the following reaction. 3. Propose a synthesis of the compounds indicated, from the given starting materials and any other needed reagents.

16 4. Which of the following is the weakest base? 5. Identify the following compound from the given spectroscopic information. C 4 7 Br 2 IR: broad peak at cm -1 and a peak at 1715 cm -1 1 NMR spectrum: Triplet, δ 1.08 (3) Multiplet, δ 2.07 (2) Triplet, δ 4.23 (1) Singlet, δ (1) 6. Predict the product(s) (if any) of each of the following reactions. a) C 3 C 2 C 2 C N + 2 b) C 6 5 -C 2 C 2 C 2 + KMn 4 d) Cl LA 2 7. For questions (a) and (b), choose the answers from the list of possible compounds shown below. a) Which compound is insoluble in water and 5% Na (aq), but is soluble in conc. 2 S 4? b) Which compound is insoluble in water, and soluble in both NaC 3(aq) and Na?